US11961998B2 - Method of producing protected anode active material particles for rechargeable lithium batteries - Google Patents
Method of producing protected anode active material particles for rechargeable lithium batteries Download PDFInfo
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- US11961998B2 US11961998B2 US16/403,826 US201916403826A US11961998B2 US 11961998 B2 US11961998 B2 US 11961998B2 US 201916403826 A US201916403826 A US 201916403826A US 11961998 B2 US11961998 B2 US 11961998B2
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- polymer
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- active material
- anode active
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- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000657 LRPu Polymers 0.000 description 1
- 229910011140 Li2C2 Inorganic materials 0.000 description 1
- 229910001216 Li2S Inorganic materials 0.000 description 1
- 229910013098 LiBF2 Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910013884 LiPF3 Inorganic materials 0.000 description 1
- 229910018688 LixC6 Inorganic materials 0.000 description 1
- 229910014652 LixSOy Inorganic materials 0.000 description 1
- 229920000079 Memory foam Polymers 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000003436 Schotten-Baumann reaction Methods 0.000 description 1
- 229910008062 Si-SiO2 Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 229910006403 Si—SiO2 Inorganic materials 0.000 description 1
- 229910006854 SnOx Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002063 Sorbothane Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 239000006263 elastomeric foam Substances 0.000 description 1
- 238000002635 electroconvulsive therapy Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical compound NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004619 high density foam Substances 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000001057 ionotropic effect Effects 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- ZVSWQJGHNTUXDX-UHFFFAOYSA-N lambda1-selanyllithium Chemical compound [Se].[Li] ZVSWQJGHNTUXDX-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229920003008 liquid latex Polymers 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000004620 low density foam Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000008210 memory foam Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002107 nanodisc Substances 0.000 description 1
- 239000002116 nanohorn Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 239000011301 petroleum pitch Substances 0.000 description 1
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- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 125000005463 sulfonylimide group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Images
Classifications
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure relates generally to the field of lithium batteries and, in particular, to polymer foam-assisted particulates containing anode active material particles for lithium batteries.
- a unit cell or building block of a lithium-ion battery is typically composed of an anode current collector, an anode or negative electrode layer (containing an anode active material responsible for storing lithium therein, a conductive additive, and a resin binder), an electrolyte and porous separator, a cathode or positive electrode layer (containing a cathode active material responsible for storing lithium therein, a conductive additive, and a resin binder), and a separate cathode current collector.
- the electrolyte is in ionic contact with both the anode active material and the cathode active material.
- a porous separator is not required if the electrolyte is a solid-state electrolyte.
- the binder in the binder layer is used to bond the anode active material (e.g. graphite or Si particles) and a conductive filler (e.g. carbon black or carbon nanotube) together to form an anode layer of structural integrity, and to bond the anode layer to a separate anode current collector, which acts to collect electrons from the anode active material when the battery is discharged.
- anode active material e.g. graphite or Si particles
- a conductive filler e.g. carbon black or carbon nanotube
- PVDF polyvinylidine fluoride
- SBR styrene-butadiene rubber
- anode current collector typically a sheet of Cu foil.
- the former three materials form a separate, discrete anode layer and the latter one forms another discrete layer.
- the most commonly used anode active materials for lithium-ion batteries are natural graphite and synthetic graphite (or artificial graphite) that can be intercalated with lithium and the resulting graphite intercalation compound (GIC) may be expressed as Li x C 6 , where x is typically less than 1.
- Graphite or carbon anodes can have a long cycle life due to the presence of a protective solid-electrolyte interface layer (SEI), which results from the reaction between lithium and the electrolyte (or between lithium and the anode surface/edge atoms or functional groups) during the first several charge-discharge cycles.
- SEI solid-electrolyte interface layer
- the lithium in this reaction comes from some of the lithium ions originally intended for the charge transfer purpose.
- the SEI As the SEI is formed, the lithium ions become part of the inert SEI layer and become irreversible, i.e. these positive ions can no longer be shuttled back and forth between the anode and the cathode during subsequent charges/discharges. Therefore, it is desirable to use a minimum amount of lithium for the formation of an effective SEI layer.
- the irreversible capacity loss Q ir can also be attributed to graphite exfoliation caused by electrolyte/solvent co-intercalation and other side reactions.
- inorganic materials that have been evaluated for potential anode applications include metal oxides, metal nitrides, metal sulfides, and the like, and a range of metals, metal alloys, and intermetallic compounds that can accommodate lithium atoms/ions or react with lithium.
- lithium alloys having a composition formula of Li a A are of great interest due to their high theoretical capacity, e.g., Li 4 Si (3,829 mAh/g), Li 4.4 Si (4,200 mAh/g), Li 4.4 Ge (1,623 mAh/g), Li 4.4 Sn (993 mAh/g), Li 3 Cd (715 mAh/g), Li 3 Sb (660 mAh/g), Li 4.4 Pb (569 mAh/g), LiZn (410 mAh/g), and Li 3 Bi (385 mAh/g).
- A is a metal or semiconductor element, such as Al and Si, and “a” satisfies 0 ⁇ a ⁇ 5) are of great interest due to their high theoretical capacity, e.g., Li 4 Si (3,829 mAh/g), Li 4.4 Si (4,200 mAh/g), Li 4.4 Ge (1,623 mAh/g), Li 4.4 Sn (993 mAh/g), Li 3 Cd (715 mAh/g), Li 3 Sb (660 mAh/g
- the coating or matrix materials used to protect active particles are carbon, sol gel graphite, metal oxide, monomer, ceramic, and lithium oxide. These protective materials are all very brittle, weak (of low strength), and/or non-conductive to lithium ions (e.g., ceramic or oxide coating).
- the protective material should meet the following requirements: (a) The protective material must be lithium ion-conducting as well as initially electron-conducting (when the anode electrode is made) and be capable of preventing liquid electrolyte from being in constant contact with the anode active material particles (e.g. Si). (b) The protective material should also have high fracture toughness or high resistance to crack formation to avoid disintegration during cycling.
- the protective material must be inert (inactive) with respect to the electrolyte, but be a good lithium ion conductor.
- the protective material must not provide any significant amount of defect sites that irreversibly trap lithium ions.
- the combined protective material-anode material structure must allow for an adequate amount of free space to accommodate volume expansion of the anode active material particles when lithiated.
- the prior art protective materials all fall short of these requirements. Hence, it was not surprising to observe that the resulting anode typically shows a reversible specific capacity much lower than expected. In many cases, the first-cycle efficiency is extremely low (mostly lower than 80% and some even lower than 60%). Furthermore, in most cases, the electrode was not capable of operating for a large number of cycles. Additionally, most of these electrodes are not high-rate capable, exhibiting unacceptably low capacity at a high discharge rate.
- Complex composite particles of particular interest are a mixture of separate Si and graphite particles dispersed in a carbon matrix; e.g. those prepared by Mao, et al. [“Carbon-coated Silicon Particle Powder as the Anode Material for Lithium Batteries and the Method of Making the Same,” US 2005/0136330 (Jun. 23, 2005)]. Also of interest are carbon matrix-containing complex nano Si (protected by oxide) and graphite particles dispersed therein, and carbon-coated Si particles distributed on a surface of graphite particles Again, these complex composite particles led to a low specific capacity or for up to a small number of cycles only.
- the prior art has not demonstrated a material that has all or most of the properties desired for use as an anode active material in a lithium-ion battery.
- a new anode active material that enables a lithium-ion battery to exhibit a high cycle life, high reversible capacity, low irreversible capacity, small particle sizes (for high-rate capacity), and compatibility with commonly used electrolytes.
- the disclosure provides an anode particulate or multiple anode particulates for a lithium battery.
- the desired particulate comprises a polymer foam material having pores and a single or a plurality of primary particles of an anode active material embedded in or in contact with the polymer foam material, wherein the primary particles of anode active material have a total solid volume Va, and the pores have a total pore volume Vp, and the volume ratio Vp/Va is from 0.1/1.0 to 10/1, preferably from 0.2/1.0 to 4.0/1.0.
- the polymer foam may be in the form of one or a plurality of pre-made polymer foam particles having a diameter or smallest dimension from 10 nm to 20 ⁇ m.
- the polymer foam may be in the form of a matrix that substantially defines the particulate size and shape, wherein the primary anode active particles are dispersed.
- the polymer foam may have a physical density from 0.005 to 1.0 g/cm 3 , typically from 0.05 to 0.5 g/cm 3 .
- the polymer foam material is selected from ethylene-vinyl acetate (EVA) foam, a copolymer of ethylene and vinyl acetate (polyethylene-vinyl acetate, PEVA), a polyethylene foam (e.g. low-density polyethylene, LDPE foam), polyimide foam, polypropylene (PP) foam, polystyrene (PS) foam (including expanded polystyrene, expanded high-impact polystyrene), polyvinyl chloride (PVC) foam; polymethacrylimide (PMI) foam, or a combination thereof.
- EVA ethylene-vinyl acetate
- PEVA polyethylene foam
- PEVA polyethylene foam
- LDPE foam low-density polyethylene
- PS polystyrene
- PMI polymethacrylimide
- the polymer foam material is preferably an elastomer foam having a high elasticity (recoverable deformation).
- elastomer foams are: (a) Nitrile rubber (NBR) foam, the copolymers of acrylonitrile (ACN) and butadiene; (b) Polychloroprene foam or Neoprene; (c) Polyurethane (PU) foam (e.g. low-resilience polyurethane, memory foam, Sorbothane, and thermoplastic polyurethane foam (TPU foam)), or a combination thereof.
- NBR Nitrile rubber
- ACN acrylonitrile
- Neoprene Neoprene
- PU Polyurethane foam
- TPU foam thermoplastic polyurethane foam
- the polymer foam material comprises a polymer selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(ethylene glycol) (PEG), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), Poly bis-methoxy ethoxyethoxide-phosphazenex, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), cyanoethyl poly(vinyl alcohol) (PVACN), aliphatic polycarbonate (including poly(vinylene carbonate) (PVC), poly(ethylene carbonate) (PEC), poly(propylene carbonate) (PPC), and poly(trimethylene carbonate) (PTMC)), single Li-ion conducting solid polymer electrolyte with a carboxylate anion, a sulfate,
- foamed polymers in a foamed particle form implemented in the vicinity of an anode active particle or in a porous matrix form in which active particles are embedded, provide a cushioning effect against volume expansion/shrinkage of the anode active material particles and also provide lithium ion-conducting channels inside the particulate, leading to a long charge/discharge cycle life even at a relatively high charge/discharge rate (e.g. >2 C or even 5 C rate).
- a rate of nC means completion of a charge or discharge procedure in (1/n) hours.
- the anode particulate further comprises a reinforcement material selected from a carbon nanotube, carbon nano-fiber, carbon or graphite fiber, graphene sheet, expanded graphite flake, polymer fibril, glass fiber, ceramic fiber, metal filament or metal nano-wire, whisker, or a combination thereof.
- a reinforcement material selected from a carbon nanotube, carbon nano-fiber, carbon or graphite fiber, graphene sheet, expanded graphite flake, polymer fibril, glass fiber, ceramic fiber, metal filament or metal nano-wire, whisker, or a combination thereof.
- the anode particulate further comprises an electron-conducting material selected from expanded graphite flakes, natural graphite flakes, exfoliated graphite worms, artificial graphite particles, sol-gel graphite, carbon, carbon nanotubes, graphene sheets, or a combination thereof.
- the anode particulate further comprises a lithium ion-conducting additive selected from lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-methanesulfonate (LiCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2 ) 2 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium nitrate (LiNO 3 ), Li-fluoroalkyl-phosphate (LiPF 3 (CF 2 CF 3 ) 3 ), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluorome
- the anode particulate further comprises a lithium ion-conducting polymer, which is different from the polymer foam material and has a room-temperature lithium-ion conductivity from 10 ⁇ 8 S/cm to 5 ⁇ 10 ⁇ 2 S/cm, more typically from 10 ⁇ 6 S/cm to 10 ⁇ 2 S/cm.
- the lithium ion-conducting polymer in the particulate may be selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(ethylene glycol) (PEG), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), Poly bis-methoxy ethoxyethoxide-phosphazenex, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), cyanoethyl poly(vinyl alcohol) (PVACN), aliphatic polycarbonate (including poly(vinylene carbonate) (PVC), poly(ethylene carbonate) (PEC), poly(propylene carbonate) (PPC), and poly(trimethylene carbonate) (PTMC)), single-ion conducting solid polymer electrolyte with a carboxylate anion, a
- a single Li-ion conducting solid polymer electrolyte may be synthesized from monomers of lithium bis (allylmalonato) borate (LiBAMB) and pentaerythritol tetrakis (2-mercaptoacetate) (PETMP) in the presence of a plasticizer, such as gamma-butyrolactone (GBL), propylene carbonate (PC) or ethylene carbonate (EC). These polymers are not generally present in a foamed polymer form inside the particulate.
- LiBAMB lithium bis (allylmalonato) borate
- PETMP pentaerythritol tetrakis (2-mercaptoacetate)
- GBL gamma-butyrolactone
- PC propylene carbonate
- EC ethylene carbonate
- the particulate further comprises a high-strength material, dispersed therein, selected from carbon nanotubes (single-walled or multi-walled CNTs), carbon nano-fibers (e.g. vapor-grown CNFs or carbonized electron-spun polymer nanofibers), carbon or graphite fibers, polymer fibrils (e.g. the aromatic polyamide fibrils extracted from aromatic polyamide fibers, such as Kevlar fibers), graphene sheets, expanded graphite flakes, glass fibers, ceramic fibers, metal filaments or metal nano-wires, whiskers (e.g. carbon whiskers, graphite whiskers, ceramic whiskers), or a combination thereof.
- An electrically conductive reinforcement is preferred.
- the anode active material may be selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Nb, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate,
- the anode active material is preferably in a form of nano particle, nano wire, nano fiber, nano tube, nano sheet, nano belt, nano ribbon, nano disc, nano platelet, or nano horn having a thickness or diameter from 0.5 nm to 100 nm.
- At least one of the anode active material particles is coated with a layer of carbon, intrinsically conducting conjugated polymer, or graphene prior to being encapsulated by a precursor to the carbon foam matrix.
- the particulate is further partially or totally encapsulated by an encapsulating shell comprising an electron-conducting material selected from a carbon, graphene, graphite, conjugated polymer, metal, or conducting composite material.
- this electron-conducting material also has a lithium ion conductivity of at least 10 ⁇ 8 S/cm, typically up to 10 ⁇ 2 S/cm.
- the present disclosure also provides a powder mass of anode particulates containing the herein invented anode particulate. Also provided is a battery anode containing the invented particulate described above. The disclosure further provides a battery containing such a battery anode.
- the battery may be a lithium-ion battery, lithium metal secondary battery, lithium-sulfur battery, lithium-air battery, or lithium-selenium battery.
- the disclosure also provides a method of producing multiple particulates containing the aforementioned anode particulate.
- the method comprises: (a) dispersing multiple primary particles of an anode active material, having a particle size from 5 nm to 20 ⁇ m, and particles of a polymer foam material, having a particle size from 50 nm to 20 ⁇ m, plus an optional adhesive or binder, in a liquid medium to form a slurry; and (b) shaping said slurry and removing said liquid medium to form said multiple particulates having a diameter from 100 nm to 50 ⁇ m.
- polymer foam particles Prior to step (a), polymer foam particles have been previously made.
- the slurry may further comprise a reinforcement material, an electron-conducting additive, a lithium ion-conducting additive, and/or an optional binder dispersed therein. This is illustrated in FIG. 3 (A) .
- Step (b) may include operating a procedure selected from pan-coating, air-suspension coating, centrifugal extrusion, vibration-nozzle encapsulation, spray-drying, coacervation-phase separation, interfacial polycondensation and interfacial cross-linking, in-situ polymerization, matrix polymerization, extrusion and pelletizing, or a combination thereof.
- the method comprises: (A) dispersing multiple primary particles of an anode active material, having a particle size from 5 nm to 20 ⁇ m, and reactive mass comprising a blowing agent and a polymer, reactive oligomer, or monomer with an initiator (plus an optional curing agent) in a liquid medium to form a slurry; (B) shaping the slurry and optionally removing the liquid medium to form reactive micro-droplets; and (C) polymerizing or curing the reactive micro-droplets and activating the blowing agent to produce the multiple particulates having a diameter from 100 nm to 50 ⁇ m.
- step (A) allows primary particles of the anode active material to be substantially dispersed in the uncured polymer or reactive monomer/oligomer mass in the micro-droplets formed in step (B).
- the anode active material particles are typically dispersed in a polymer foam matrix inside the particulate.
- the slurry may further comprise a reinforcement material, an electron-conducting additive, and/or a lithium ion-conducting additive dispersed therein.
- a curing or crosslinking agent may be used to produce a lightly crosslinked polymer or elastomer to impart a high elasticity (large, recoverable elastic deformation) to the polymer foam.
- Step (B) may include operating a procedure selected from pan-coating, air-suspension coating, centrifugal extrusion, vibration-nozzle encapsulation, spray-drying, coacervation-phase separation, interfacial polycondensation and interfacial cross-linking, in-situ polymerization, matrix polymerization, extrusion and pelletizing, or a combination thereof.
- the method may further comprise an encapsulating step to partially or totally encapsulate the particulate with an electron-conducting material selected from carbon, graphene, graphite, conjugated polymer, metal, or conducting composite material.
- an electron-conducting material selected from carbon, graphene, graphite, conjugated polymer, metal, or conducting composite material.
- the encapsulating step may include an operation selected from physical vapor deposition, chemical vapor deposition, sputtering, polymer coating and pyrolyzation, coating of a conjugated polymer, ball-milling, spray drying, pan-coating, air-suspension coating, centrifugal extrusion, or vibration-nozzle encapsulation.
- the encapsulating step may comprise operating (i) an air-jet milling procedure to embrace the particulates with natural flake graphite or (ii) a ball milling procedure to embrace the particulates with expanded graphite flakes, exfoliated graphite worms, or graphene sheets.
- expanded graphite flakes are typically produced by using mechanical shearing means (e.g. disperser machine, mechanical shearing machine, rotating-blade mixer, ultrasonicator, air jet mill, etc.) to break up the exfoliated graphite worms.
- the ball milling operating procedure may comprise operating an apparatus selected from a vibratory ball mill, planetary ball mill, high energy mill, basket mill, agitator ball mill, cryogenic ball mill, microball mill, tumbler ball mill, continuous ball mill, stirred ball mill, pressurized ball mill, attritor, plasma-assisted ball mill, freezer mill, vibratory sieve, bead mill, nano bead mill, ultrasonic homogenizer mill, centrifugal planetary mixer, vacuum ball mill, or resonant acoustic mixer.
- an apparatus selected from a vibratory ball mill, planetary ball mill, high energy mill, basket mill, agitator ball mill, cryogenic ball mill, microball mill, tumbler ball mill, continuous ball mill, stirred ball mill, pressurized ball mill, attritor, plasma-assisted ball mill, freezer mill, vibratory sieve, bead mill, nano bead mill, ultrasonic homogenizer mill, centrifugal planetary mixer, vacuum ball mill, or resonant acoustic mixer
- the method may further comprise a step of incorporating the particulates into an anode electrode of a lithium battery and a step of incorporating such an anode into a battery.
- the particles of anode active material contain pre-lithiated particles.
- these particles have been previously intercalated with Li ions (e.g. via electrochemical charging) up to an amount of 0.1% to 47% by weight of Li.
- the particles of anode active material prior to being combined with a polymer foam, contain primary particles pre-coated with a coating layer of a conductive material selected from carbon, pitch, carbonized resin, a conductive polymer, a conductive organic material, a metal coating, a metal oxide shell, graphene sheets, or a combination thereof.
- the coating layer thickness is preferably in the range from 1 nm to 20 ⁇ m, preferably from 10 nm to 10 ⁇ m, and further preferably from 100 nm to 1 ⁇ m.
- the particulates comprise a reinforcement material, a lithium-ion-conducting additive, or both that are dispersed therein.
- the reinforcement material may contain a high-strength material selected from carbon nanotubes (single-walled or multi-walled CNTs), carbon nano-fibers (e.g. vapor-grown CNFs or carbonized electron-spun polymer nanofibers), carbon or graphite fibers, polymer fibrils (e.g. the aromatic polyamide fibrils extracted from aromatic polyamide fibers, such as Kevlar fibers), graphene sheets, expanded graphite flakes, glass fibers, ceramic fibers, metal filaments or metal nano-wires, whiskers (e.g. carbon whiskers, graphite whiskers, ceramic whiskers), or a combination thereof.
- a high-strength material selected from carbon nanotubes (single-walled or multi-walled CNTs), carbon nano-fibers (e.g. vapor-grown CNFs or carbonized electron-spun
- the particles of anode active material may be selected from the group consisting of: (A) lithiated and un-lithiated silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (B) lithiated and un-lithiated alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (C) lithiated and un-lithiated oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Nb, Co, or Cd, and their mixtures, composites, or lithium-containing composites; (D
- the anode active material particles include powder, flakes, beads, pellets, spheres, wires, fibers, filaments, discs, ribbons, or rods, having a diameter or thickness from 2 nm to 20 ⁇ m.
- the diameter or thickness is from 10 nm to 100 nm.
- FIG. 1 (A) Schematic of a particulate comprising a polymer foam matrix, at least a primary anode material particle and a conductive additive that are dispersed in the polymer foam matrix.
- FIG. 1 (B) Schematic of a particulate comprising polymer foam particles, at least a primary anode material particle in contact with a polymer foam particle, and a conductive additive.
- An adhesive or binder (not shown) may be used to bond these ingredients together.
- FIG. 2 (A) Schematic illustrating the notion that expansion of Si particles, upon lithium intercalation during charging of a prior art lithium-ion battery, can lead to pulverization of Si particles, interruption of the conductive paths formed by the conductive additive, and loss of contact with the current collector;
- FIG. 2 (B) illustrates the issues associated with prior art anode active material; for instance, a non-lithiated Si particle encapsulated by a protective shell (e.g. carbon shell) in a core-shell structure inevitably leads to breakage of the shell and that a pre-lithiated Si particle encapsulated with a protective layer leads to poor contact between the contracted Si particle and the rigid protective shell during battery discharge.
- a protective shell e.g. carbon shell
- FIG. 3 (A) A diagram showing the presently invented process for producing anode particulates of FIG. 1 (B) , containing foamed polymer particles and anode active material particles according to an embodiment of the disclosure.
- FIG. 3 (B) A diagram showing the presently invented process for producing anode particulates of FIG. 1 (A) , containing foamed polymer matrix and anode active material particles and an electron-conducting reinforcement material dispersed in the foamed matrix according to another embodiment of the disclosure.
- FIG. 3 (C) Some examples of porous primary particles of an anode active material.
- FIG. 4 The charge-discharge cycling behaviors of 2 lithium cells featuring Co 3 O 4 particle-based anodes: one cell containing expanded graphite-embraced solid polymer-Co 3 O 4 particles (substantially no pores) and the other cell containing expanded graphite-encapsulated, polymer foam-protected Co 3 O 4 particles (having a pore-to-anode particle volume ratio of 1.3/1.0).
- FIG. 5 The specific capacity values of 3 lithium-ion cells having SnO 2 particles as the an anode active material: one cell featuring exfoliated graphite worm-encapsulated SnO 2 particles having no pores between encapsulating exfoliated graphite worm layer and SnO 2 particles; second cell having a polymer foam between the encapsulating exfoliated graphite worm layer and SnO 2 particles with a pore-to-SnO 2 volume ration of 0.45/1.0; third cell having a polymer foam between the encapsulating graphene sheets and SnO 2 particles with a pore-to-SnO 2 volume ration of 1.25/1.0.
- FIG. 6 Specific capacities of 2 lithium-ion cells having a core of Si nanowires (SiNW) embedded in an expanded graphite flake-reinforced carbon foam matrix having a pore-to-Si volume ratio of 1.85/1.0 and the other a pore-to-Si volume ratio of 0.62/1.0.
- FIG. 7 Cycle life of lithium-ion cell containing expanded graphite flake-encapsulated, CNT-reinforced polymer foam protected porous Si particles, plotted as a function of the total pore-to-solid ratio in the particulate.
- a lithium-ion battery cell is typically composed of an anode current collector (e.g. Cu foil), an anode or negative electrode active material layer (i.e. anode layer typically containing particles of an anode active material, conductive additive, and binder), a porous separator and/or an electrolyte component, a cathode or positive electrode active material layer (containing a cathode active material, conductive additive, and resin binder), and a cathode current collector (e.g. Al foil). More specifically, the anode layer is composed of particles of an anode active material (e.g. graphite, Sn, SnO 2 , or Si), a conductive additive (e.g. carbon black particles), and a resin binder (e.g. SBR or PVDF). This anode layer is typically 50-300 ⁇ m thick (more typically 100-200 ⁇ m) to give rise to a sufficient amount of current per unit electrode area.
- an anode current collector e.g. Cu foil
- the anode can be designed to contain higher-capacity anode active materials having a composition formula of Li a A (A is a metal or semiconductor element, such as Al and Si, and “a” satisfies 0 ⁇ a ⁇ 5).
- A is a metal or semiconductor element, such as Al and Si, and “a” satisfies 0 ⁇ a ⁇ 5).
- the presence of embracing graphene sheets enables the formation of a porous carbon structure between these graphene sheets and primary anode particles (e.g. Si and SiO x particles, 0 ⁇ x ⁇ 2.0), derived from carbonization of the polymer matrix or coating that embeds the anode primary particles.
- primary anode particles e.g. Si and SiO x particles, 0 ⁇ x ⁇ 2.0
- the polymer coating or matrix tends to form solid (relatively pore-free) carbon material when the polymer is pyrolyzed.
- the disclosure provides an anode particulate or multiple anode particulates for a lithium battery.
- the particulate or at least one of the multiple particulates comprises a polymer foam material having pores and a single or a plurality of primary particles of an anode active material embedded in or in contact with the polymer foam material, wherein the primary particles of anode active material have a total solid volume Va, and the pores have a total pore volume Vp, and the volume ratio Vp/Va is from 0.1/1.0 to 10/1, preferably from 0.2/1.0 to 4.0/1.0.
- the polymer foam may be in the form of one or a plurality of pre-made polymer foam particles having a particle diameter or smallest dimension from 10 nm to 20 ⁇ m, along with primary particle(s) of an anode active material and a conductive additive (e.g. carbon nanotubes, carbon nano-fibers, graphene sheets, expanded graphite sheets, conducting polymer, etc.).
- An adhesive or binder may be used to bond these ingredients together to form a particulate of structural integrity.
- Each particulate may contain therein one or a plurality of polymer foam particles.
- the polymer foam may be in the form of a matrix that substantially defines the particulate size and shape, wherein the primary anode active particles are dispersed in this polymer foam matrix.
- an encapsulating shell is implemented to partially or totally embrace a particulate.
- Such an encapsulating shell may contain an electron-conducting material (e.g. carbon, graphene, etc.), a lithium ion-conducting material (e.g. a polymer commonly used as a solid polymer electrolyte), or a material that is both electron-conducting and ion-conducting (e.g. sulfonated conjugated polymers).
- Vp/Va ratio Although there is no theoretical upper limit to either the Vp/Va ratio, too large a ratio means too low an electrode packing density and, hence, a lower volumetric energy density of the resulting lithium cell.
- a practical upper limit for the Vp/Va ratio is 20/1.0, more preferably 10/1.0, and most preferably 5.0/1.0.
- a practical lower limit is 0.1/1.0, but typically >0.2/1.0, and more typically and desirably >0.3/1.0
- the particulate is reinforced with a high-strength material selected from carbon nanotubes (single-walled or multi-walled CNTs), carbon nano-fibers (e.g. vapor-grown CNFs or carbonized electron-spun polymer nanofibers), carbon or graphite fibers, polymer fibrils (e.g. the aromatic polyamide fibrils extracted from aromatic polyamide fibers, such as Kevlar fibers), graphene sheets, expanded graphite flakes, glass fibers, ceramic fibers, metal filaments or metal nano-wires, whiskers (e.g. carbon whiskers, graphite whiskers, ceramic whiskers), or a combination thereof.
- a high-strength material selected from carbon nanotubes (single-walled or multi-walled CNTs), carbon nano-fibers (e.g. vapor-grown CNFs or carbonized electron-spun polymer nanofibers), carbon or graphite fibers, polymer fibrils (e.g. the aromatic polyamide fibrils extracted from aromatic
- the anode active material is a high-capacity anode active material having a specific lithium storage capacity greater than 372 mAh/g (which is the theoretical capacity of graphite).
- the anode particulate may be further encapsulated by an encapsulating shell comprising an electron-conducting material (e.g. carbon, metal, conducting composite), lithium ion-conducting material (e.g. a polymer commonly used in a gel electrolyte or solid state electrolyte), and a material that is both electron-conducting and lithium-ion conducting (e.g. amorphous carbon, graphene, and conjugated polymer).
- an electron-conducting material e.g. carbon, metal, conducting composite
- lithium ion-conducting material e.g. a polymer commonly used in a gel electrolyte or solid state electrolyte
- a material that is both electron-conducting and lithium-ion conducting e.g. amorphous carbon, graphene, and conjugated polymer
- the primary anode active material particles may be porous, having surface pores or internal pores, as schematically illustrated in FIG. 3 (C) .
- the production methods of porous solid particles are well-known in the art.
- the production of porous Si particles may be accomplished by etching particles of a Si—Al alloy using HCl solution (to remove the Al element leaving behind pores) or by etching particles of a Si—SiO 2 mixture using HF solution (by removing SiO 2 to create pores).
- Porous SnO 2 nano particles may be synthesized by a modified procedure described by Gurunathan et al [P. Gurunathan, P. M. Ette and K. Ramesha, ACS Appl. Mater. Inter., 6 (2014) 16556-16564].
- a typical synthesis procedure 8.00 g of SnCl 2 .6H 2 O, 5.20 g of resorcinol and 16.0 mL of 37% formaldehyde solution were mixed in 160 mL of H 2 O for about 30 minutes.
- the solution is sealed in a 250 mL round-bottom flask and kept in water bath at 80° C. for 4 hours.
- the resulting red gel is dried at 80° C. in an oven and calcined at 700° C. for 4 hours in N 2 and air atmosphere in sequence.
- the obtained white SnO 2 may be mechanically ground into finer powder for 30-60 minutes in mortar.
- porous anode active material particles may be produced by depositing the anode active material onto surfaces or into pores of a sacrificial material structure, followed by removing the sacrificial material.
- a deposition can be conducted using CVD, plasma-enhanced CVD, physical vapor deposition, sputtering, solution deposition, melt impregnation, chemical reaction deposition, etc.
- This amount of pore volume inside the particulate (in the core portion, including the surface/internal pores of a primary particle and the pores that are not part of a primary particle) provides empty space to accommodate the volume expansion of the anode active material so that the thin encapsulating layer would not significantly expand (not to exceed 50% volume expansion of the particulate) when the lithium battery is charged.
- the particulate does not increase its volume by more than 20%, further preferably less than 10% and most preferably by approximately 0% when the lithium battery is charged. This can be accomplished by making the ratio of total pore volume-to-solid anode particle volume to be in the range from 0.3/1.0 to 4.0/1.0.
- the total pore volume includes the pores associated with a primary particle and those pores not part of a primary particle.
- Such a constrained volume expansion of the particulate would not only reduce or eliminate the volume expansion of the anode electrode but also reduce or eliminate the issue of repeated formation and destruction of a solid-electrolyte interface (SEI) phase.
- SEI solid-electrolyte interface
- Carbon materials can assume an essentially amorphous structure (glassy carbon), a highly organized crystal (graphite), or a whole range of intermediate structures that are characterized in that various proportions and sizes of graphite crystallites and defects are dispersed in an amorphous matrix.
- a graphite crystallite is composed of a number of graphene sheets or basal planes that are bonded together through van der Waals forces in the c-axis direction, the direction perpendicular to the basal plane. These graphite crystallites are typically micron- or nanometer-sized.
- the graphite crystallites are dispersed in or connected by crystal defects or an amorphous phase in a graphite particle, which can be a graphite flake, carbon/graphite fiber segment, carbon/graphite whisker, or carbon/graphite nano-fiber.
- a graphite particle which can be a graphite flake, carbon/graphite fiber segment, carbon/graphite whisker, or carbon/graphite nano-fiber.
- graphene planes hexagonal lattice structure of carbon atoms
- the processes for producing exfoliated graphite worms and subsequently separated expanded graphite flakes typically involve immersing natural or artificial graphite powder in a mixture of concentrated sulfuric acid, nitric acid, and an oxidizer, such as potassium permanganate or sodium perchlorate. It typically requires 5-120 hours to complete the chemical intercalation/oxidation reaction. Once the reaction is completed, the slurry is subjected to repeated steps of rinsing and washing with water and then subjected to drying treatments to remove water. The dried powder is commonly referred to as graphite intercalation compound (GIC) or graphite oxide (GO).
- GIC graphite intercalation compound
- GO graphite oxide
- a graphite worm is a bulk graphite entity that is composed of interconnected graphite flakes having large spaces between flakes. The flakes are typically composed of >100 graphene planes (>35 nm in thickness) and they are interconnected together to form a fluffy, worm-like morphology (please see the SEM image inserted in FIG. 1 ).
- graphite worms can be broken up into separated/isolated expanded graphite flakes. High-intensity mechanical shearing can lead to the formation of graphene sheets instead.
- the disclosure also provides a method of producing multiple particulates containing the aforementioned anode particulate.
- the method comprises: (a) dispersing multiple primary particles of an anode active material, having a particle size from 5 nm to 20 ⁇ m, and particles of a polymer foam material, having a particle size from 50 nm to 20 ⁇ m, plus an optional adhesive or binder, in a liquid medium to form a slurry; and (b) shaping said slurry and removing said liquid medium to form said multiple particulates having a diameter from 100 nm to 50 ⁇ m.
- polymer foam particles Prior to step (a), polymer foam particles have been previously made.
- the slurry may further comprise a reinforcement material, an electron-conducting additive, a lithium ion-conducting additive, and/or an optional binder dispersed therein.
- Step (b) may include operating a procedure selected from pan-coating, air-suspension coating, centrifugal extrusion, vibration-nozzle encapsulation, spray-drying, coacervation-phase separation, interfacial polycondensation and interfacial cross-linking, in-situ polymerization, matrix polymerization, extrusion and pelletizing, or a combination thereof.
- the method comprises: (A) dispersing multiple primary particles of an anode active material, having a particle size from 5 nm to 20 ⁇ m, and reactive mass comprising a blowing agent and a polymer, reactive oligomer, or monomer with an initiator (plus an optional curing agent) in a liquid medium to form a slurry; (B) shaping the slurry and optionally removing the liquid medium to form reactive micro-droplets; and (C) polymerizing or curing the reactive micro-droplets and activating the blowing agent to produce the multiple particulates having a diameter from 100 nm to 50 ⁇ m.
- step (A) allows primary particles of the anode active material to be substantially dispersed in the uncured polymer or reactive monomer/oligomer mass in the micro-droplets formed in step (B).
- the anode active material particles are typically dispersed in a polymer foam matrix inside the particulate.
- the slurry may further comprise a reinforcement material, an electron-conducting additive, and/or a lithium ion-conducting additive dispersed therein.
- a curing or crosslinking agent may be used to produce a lightly crosslinked polymer or elastomer to impart a high elasticity (large, recoverable elastic deformation) to the polymer foam.
- step (B) may include operating a procedure selected from pan-coating, air-suspension coating, centrifugal extrusion, vibration-nozzle encapsulation, spray-drying, coacervation-phase separation, interfacial polycondensation and interfacial cross-linking, in-situ polymerization, matrix polymerization, extrusion and pelletizing, or a combination thereof to produce said multiple polymer-coated primary particles of an anode active material.
- the method may further comprise an encapsulating step to partially or totally encapsulate the particulate with an electron-conducting material (selected from a carbon, graphene, expanded graphite, conjugated polymer, metal, or conducting composite material) and/or a lithium ion-conducting material (polymer for gel electrolyte or solid polymer electrolyte, sulfonated polymer, disordered carbon, etc.).
- an electron-conducting material selected from a carbon, graphene, expanded graphite, conjugated polymer, metal, or conducting composite material
- a lithium ion-conducting material polymer for gel electrolyte or solid polymer electrolyte, sulfonated polymer, disordered carbon, etc.
- expanded graphite flakes are typically produced by using mechanical shearing means (e.g. disperser machine, mechanical shearing machine, rotating-blade mixer, ultrasonicator, air jet mill, etc.) to break up the exfoliated graphite worms.
- mechanical shearing means e.g. disperser machine, mechanical shearing machine, rotating-blade mixer, ultrasonicator, air jet mill, etc.
- the ball milling operating procedure may comprise operating an apparatus selected from a vibratory ball mill, planetary ball mill, high energy mill, basket mill, agitator ball mill, cryogenic ball mill, microball mill, tumbler ball mill, continuous ball mill, stirred ball mill, pressurized ball mill, attritor, plasma-assisted ball mill, freezer mill, vibratory sieve, bead mill, nano bead mill, ultrasonic homogenizer mill, centrifugal planetary mixer, vacuum ball mill, or resonant acoustic mixer.
- an apparatus selected from a vibratory ball mill, planetary ball mill, high energy mill, basket mill, agitator ball mill, cryogenic ball mill, microball mill, tumbler ball mill, continuous ball mill, stirred ball mill, pressurized ball mill, attritor, plasma-assisted ball mill, freezer mill, vibratory sieve, bead mill, nano bead mill, ultrasonic homogenizer mill, centrifugal planetary mixer, vacuum ball mill, or resonant acoustic mixer
- a blowing agent or foaming agent is a substance which is capable of producing a cellular or foamed structure via a foaming or pore-forming process in a variety of materials that undergo hardening or phase transition, such as polymers (plastics and rubbers). Blowing agents or related pore-forming mechanisms to create pores or cells (bubbles) in a structure for producing a porous or cellular material, can be classified into the following groups:
- the particulates preferably contain those anode active materials capable of storing lithium ions greater than 372 mAh/g, theoretical capacity of natural graphite.
- these high-capacity anode active materials are Si, Ge, Sn, SnO 2 , SiO x , Co 3 O 4 , etc.
- these materials if implemented in the anode, have the tendency to expand and contract when the battery is charged and discharged.
- the expansion and contraction of the anode active material can lead to expansion and contraction of the anode, causing mechanical instability of the battery cell.
- repeated expansion/contraction of particles of Si, Ge, Sn, SiO x , SnO 2 , Co 3 O 4 , etc. quickly leads to pulverization of these particles and rapid capacity decay of the electrode.
- the particles of solid anode active material may contain pre-lithiated particles.
- the electrode active material particles such as Si, Ge, Sn, SnO 2 , Co 3 O 4 , etc.
- these particles have already been previously intercalated with Li ions (e.g. via electrochemical charging).
- the particles of anode electrode active material contain particles that have been pre-coated with a coating of a conductive material selected from carbon, pitch, carbonized resin, a conductive polymer, a conductive organic material, a graphene coating (e.g. graphene sheets), a metal coating, a metal oxide shell, or a combination thereof.
- the coating layer thickness is preferably in the range from 1 nm to 10 ⁇ m, preferably from 2 nm to 1 ⁇ m, and further preferably from 5 nm to 100 nm. This coating is implemented for the purpose of establishing a stable solid-electrolyte interface (SEI) to increase the useful cycle life of a lithium-ion battery.
- SEI solid-electrolyte interface
- the particles of solid anode active material contain particles that are, prior to being combined with polymer foam, pre-coated with a carbon precursor material selected from a coal tar pitch, petroleum pitch, meso-phase pitch, polymer, organic material, or a combination thereof so that the carbon precursor material resides between surfaces of the solid electrode active material particles and the graphite matrix, and the method further contains a step of heat-treating the polymer-coated anode active material particles to convert the carbon precursor material to a carbon backbone material.
- a carbon precursor material selected from a coal tar pitch, petroleum pitch, meso-phase pitch, polymer, organic material, or a combination thereof
- the same carbon precursor coating procedure may be applied to encapsulate the particulates (already containing anode active material primary particles and polymer foam).
- the resulting precursor-encapsulated particulates may then be heat-treated to convert the encapsulating shell into a carbon shell.
- the carbon material can help to completely seal off the particulate to prevent direct contact of the embraced anode active material with liquid electrolyte, which otherwise could continue to form additional SEI, thereby continuously consuming the lithium ions or solvent in the electrolyte, leading to rapid capacity decay.
- the method further comprises a step of exposing the particulates to CVD carbon, PVD carbon, sputtering carbon or metal oxide, or a liquid or vapor of a conductive material that is conductive to electrons and/or ions of lithium.
- This procedure of generating an encapsulating shell serves to provide a stable SEI or to make the SEI more stable.
- the particles of anode active material may be selected from the group consisting of: (A) lithiated and un-lithiated silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (B) lithiated and un-lithiated alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (C) lithiated and un-lithiated oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Nb, Co, or Cd, and their mixtures, composites, or lithium-containing composites; (D
- Anode active material particles and polymer foam particles may be made into micro-droplets and/or the micro-droplets may be encapsulated by a shell using a micro-encapsulation procedure.
- micro-encapsulation methods there are three broad categories of micro-encapsulation methods that can be implemented to produce particulate: physical methods, physico-chemical methods, and chemical methods.
- the physical methods include pan-coating, air-suspension coating, centrifugal extrusion, vibration nozzle, and spray-drying methods.
- the physico-chemical methods include ionotropic gelation and coacervation-phase separation methods.
- the chemical methods include interfacial polycondensation, interfacial cross-linking, in-situ polymerization, and matrix polymerization.
- Pan-coating method The pan coating process involves tumbling the active material particles (along with other ingredients, such as polymer foam particles, additive, and/or reinforcement materials) in a pan or a similar device while the encapsulating material, or matrix material, or an adhesive/binder material (e.g. elastomer monomer/oligomer, polymer melt, polymer/solvent solution, along with a blowing agent when desired) is applied slowly until a desired encapsulating shell thickness or a desired amount of matrix material or adhesive material is attained.
- active material particles along with other ingredients, such as polymer foam particles, additive, and/or reinforcement materials
- an adhesive/binder material e.g. elastomer monomer/oligomer, polymer melt, polymer/solvent solution, along with a blowing agent when desired
- Air-suspension coating method In the air suspension coating process, the solid particles (core materials, such as anode particles, foamed polymer particles, additive/reinforcement materials, etc.) are dispersed into the supporting air stream in an encapsulating chamber. A controlled stream of a polymer-solvent solution (e.g. elastomer or its monomer or oligomer dissolved in a solvent; or its monomer or oligomer alone in a liquid state) is concurrently introduced into this chamber, allowing the solution to hit and coat the suspended particles. These suspended particles are encapsulated (fully coated) with polymers while the volatile solvent is removed, leaving a thin layer of polymer (e.g.
- a polymer-solvent solution e.g. elastomer or its monomer or oligomer dissolved in a solvent; or its monomer or oligomer alone in a liquid state
- elastomer or its precursor which is cured/hardened subsequently on surfaces of these particles. This process may be repeated several times until the required parameters, such as full-coating thickness (i.e. encapsulating shell or wall thickness), are achieved.
- the air stream which supports the particles also helps to dry them, and the rate of drying is directly proportional to the temperature of the air stream, which can be adjusted for optimized shell thickness.
- the particles in the encapsulating zone portion may be subjected to re-circulation for repeated coating.
- the encapsulating chamber is arranged such that the particles pass upwards through the encapsulating zone, then are dispersed into slower moving air and sink back to the base of the encapsulating chamber, enabling repeated passes of the particles through the encapsulating zone until the desired encapsulating shell thickness is achieved.
- Centrifugal extrusion Anode active materials may be encapsulated using a rotating extrusion head containing concentric nozzles.
- a stream of core fluid slurry containing particles of an anode active material and other ingredients dispersed in a solvent
- the suspension may also contain a conducting reinforcement material.
- the device rotates and the stream moves through the air it breaks, due to Rayleigh instability, into droplets of core, each coated with the shell solution. While the droplets are in flight, the molten shell may be hardened or the solvent may be evaporated from the shell solution. If needed, the capsules can be hardened after formation by catching them in a hardening bath.
- Vibrational nozzle encapsulation method Core-shell encapsulation or matrix-encapsulation of an anode active material (along with a reinforcement material, for instance) can be conducted using a laminar flow through a nozzle and vibration of the nozzle or the liquid. The vibration has to be done in resonance with the Rayleigh instability, leading to very uniform droplets.
- the liquid can consist of any liquids with limited viscosities (1-50,000 mPa ⁇ s): emulsions, suspensions or slurry containing the anode active material.
- the solidification can be done according to the used gelation system with an internal gelation (e.g. sol-gel processing, melt) or an external (additional binder system, e.g. in a slurry).
- Spray drying may be used to encapsulate particulates of an active material or to produce the particulates per se when desired ingredients are dissolved or suspended in a melt or polymer solution to form a suspension.
- the suspension may also contain anode particles, polymer foam particles, an optional reinforcement material, etc.
- the liquid feed solution or suspension
- the liquid feed is atomized to form droplets which, upon contacts with hot gas, allow solvent to get vaporized and thin polymer shell to fully embrace the solid particles of the active material.
- Coacervation-phase separation This process consists of three steps carried out under continuous agitation:
- Interfacial polycondensation entails introducing the two reactants to meet at the interface where they react with each other. This is based on the concept of the Schotten-Baumann reaction between an acid chloride and a compound containing an active hydrogen atom (such as an amine or alcohol), polyester, polyurea, polyurethane, or urea-urethane condensation. Under proper conditions, thin flexible encapsulating shell (wall) forms rapidly at the interface. A solution of the anode active material and a diacid chloride are emulsified in water and an aqueous solution containing an amine and a polyfunctional isocyanate is added.
- an active hydrogen atom such as an amine or alcohol
- a base may be added to neutralize the acid formed during the reaction.
- Condensed polymer shells form instantaneously at the interface of the emulsion droplets.
- Interfacial cross-linking is derived from interfacial polycondensation, wherein cross-linking occurs between growing polymer chains and a multi-functional chemical groups to form an elastomer shell material.
- In-situ polymerization In some micro-encapsulation processes, active materials particles are fully coated with a monomer or oligomer first. Then, direct polymerization of the monomer or oligomer is carried out on the surfaces of these material particles.
- Matrix polymerization This method involves dispersing and embedding a core material in a polymeric matrix during formation of the particles. This can be accomplished via spray-drying, in which the particles are formed by evaporation of the solvent from the matrix material. Another possible route is the notion that the solidification of the matrix is caused by a chemical change.
- Extrusion and pelletizing One may simply mix anode active material particles (with or without graphene sheets or other conducting material pre-embraced around the particles) and polymer together (through blending, melt mixing, or solution mixing) to form a mixture that is extruded out of an extruder slit or spinneret holes to form rods or filaments of an anode particle-embedded polymer composite. Upon solidification, the composite rods or filaments may be cut into smaller particles using pelletizer, ball mill, etc.
- the anode active material particles include powder, flakes, beads, pellets, spheres, wires, fibers, filaments, discs, ribbons, or rods, having a diameter or thickness from 2 nm to 20 ⁇ m.
- the diameter or thickness is from 10 nm to 100 nm.
- exfoliated graphite worms and/or expanded graphite flakes, along with primary particles of an anode active material may be mixed and charged into a chamber of an impact energy device.
- the energy impacting apparatus may be a vibratory ball mill, planetary ball mill, high energy mill, basket mill, agitator ball mill, cryogenic ball mill, microball mill, tumbler ball mill, continuous ball mill, stirred ball mill, pressurized ball mill, attritor, plasma-assisted ball mill, freezer mill, vibratory sieve, bead mill, nanobead mill, ultrasonic homogenizer mill, centrifugal planetary mixer, vacuum ball mill, or resonant acoustic mixer.
- the energy impacting apparatus may be operated to produce graphite-embraced, polymer-protected anode particles.
- the embracing graphite matrix in this product comprises expanded graphite flakes that are typically thicker than 35 nm, in contrast to single-layer graphene or few-layer graphene that has a thickness approximately from 0.34 nm to 3.4 nm.
- Example 1 Various Blowing Agents and Pore-Forming (Bubble-Producing) Processes
- blowing agents are mixed into the plastic pellets in the form of powder or pellets and dissolved at higher temperatures. Above a certain temperature specific for blowing agent dissolution, a gaseous reaction product (usually nitrogen or CO 2 ) is generated, which acts as a blowing agent.
- a gaseous reaction product usually nitrogen or CO 2
- Chemical foaming agents can be organic or inorganic compounds that release gasses upon thermal decomposition. CFAs are typically used to obtain medium- to high-density foams, and are often used in conjunction with physical blowing agents to obtain low-density foams. CFAs can be categorized as either endothermic or exothermic, which refers to the type of decomposition they undergo. Endothermic types absorb energy and typically release carbon dioxide and moisture upon decomposition, while the exothermic types release energy and usually generate nitrogen when decomposed. The overall gas yield and pressure of gas released by exothermic foaming agents is often higher than that of endothermic types. Endothermic CFAs are generally known to decompose in the range from 130° C. to 230° C.
- CFAs decompose around 200° C. (392° F.).
- activation (decomposition) temperatures of CFAs fall into the range of our heat treatment temperatures.
- suitable chemical blowing agents include sodium bicarbonate (baking soda), hydrazine, hydrazide, azodicarbonamide (exothermic chemical blowing agents), nitroso compounds (e.g. N, N-Dinitroso pentamethylene tetramine), hydrazine derivatives (e.g. 4, 4′-Oxybis (benzenesulfonyl hydrazide) and Hydrazo dicarbonamide), and hydrogen carbonate (e.g. sodium hydrogen carbonate).
- baking soda hydrazine
- hydrazide azodicarbonamide
- nitroso compounds e.g. N, N-Dinitroso pentamethylene tetramine
- hydrazine derivatives e.g. 4, 4′-Oxybis (benzenesulfon
- blowing agents include Carbon dioxide (CO 2 ), Nitrogen (N 2 ), Isobutane (C 4 H 10 ), Cyclopentane (C 5 H 10 ), Isopentane (C 5 H 12 ), CFC-11 (CFCI 3 ), HCFC-22 (CHF 2 CI), HCFC-142b (CF 2 CICH 3 ), and HCFC-134a (CH 2 FCF 3 ).
- CO 2 Carbon dioxide
- Nitrogen N 2
- Isobutane C 4 H 10
- Cyclopentane C 5 H 10
- Isopentane C 5 H 12
- CFC-11 CFCI 3
- HCFC-22 CHF 2 CI
- HCFC-142b HCFC-142b
- HCFC-134a CH 2 FCF 3
- chlorofluorocarbons are also not environmentally safe and therefore already forbidden in many countries.
- the alternatives are hydrocarbons, such as isobutane and pentane, and the gases such as CO 2 and nitrogen.
- the blowing agent amount introduced into the polymer in terms of a blowing agent-to-polymer material weight ratio, is typically from 0/1.0 to 1.0/1.0, preferably from 0.2/1.0 to 0.8/1.0.
- Example 2 Anode Particulates Comprising Expanded Graphite Flakes, Anode Particles and Polymer Foam
- anode active materials in a fine powder form were investigated. These include Co 3 O 4 , Si, Ge, SiO x (0 ⁇ x ⁇ 2), etc., which are used as examples to illustrate the best mode of practice. These active materials were either prepared in house or purchased from commercial sources. Primary particles of an anode active material, expanded graphite (EP) flakes, and a small but controlled amount of a blowing agent (e.g. baking soda; the proportion depending upon the porosity level desired) were dispersed in a polymer-solvent solution (e.g. Polyvinyl pyrrolidone, PVP, + water) to form a slurry, which was spray-dried to form micro-droplets.
- a polymer-solvent solution e.g. Polyvinyl pyrrolidone, PVP, + water
- a mass of these micro-droplets containing a blowing agent was activated at approximately 150° C. to obtain anode particulates comprising anode particles and EP flakes (as an example of a conductive reinforcement material) dispersed in a porous PVP matrix.
- Example 3 Reinforced Polymer Foam-Assisted Sn, SiO x , and Ge Particles
- polymer foam particles were made first, and then size-reduced and combined with several different anode active materials and different reinforcement materials to form the desired particulates.
- the conductive reinforcement materials used in this study include graphene oxide sheets, expanded graphite flakes, and CNTs.
- a more desired proportion of a conductive reinforcement is found to be from 2/100 to 20/100.
- the polymers used in the present study were water soluble polymers, including polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), and polyacrylic acid (PAA), and the solvent used was water.
- bating soda was used as a blowing agent.
- the selected polymer and a desired amount of baking soda were dissolved in water to form a polymer solution containing up to 5% solid content.
- the polymer solution was then spray-dried to form micro-droplets, comprising a polymer and a blowing agent.
- the micro-droplets were then heated to produce polymer foam particles at a temperature above the blowing agent activation temperature and typically ⁇ 20 to +10 within the melting temperature or glass transition temperature of a polymer.
- the polymer foam particles typically have a diameter or shortest dimension from 2 to 150 ⁇ m, which could be reduced to mostly smaller than 5 ⁇ m in size.
- Polymer foam particles, primary particles of an anode active material and a reinforcement material at a desired ratio were then dispersed in a liquid medium to form a slurry, which was then spray-dried to obtain anode particulates, each containing one or a plurality of anode active particles, one or a plurality of polymer foam particles, and some amount of conductive additives (e.g. CNTs, RGO sheets, etc.).
- conductive additives e.g. CNTs, RGO sheets, etc.
- thermoplastic urethane foam precursor (Sunko Chemicals Co. Taiwan) using pan-coating to obtain thermoplastic polyurethane-coated/embedded particles.
- the blowing agent was activated during and subsequent to the pan-coating procedure to obtain porous droplets. Airjet milling was used to further reduce the size of the droplets to approximately 4-55 ⁇ m.
- particulates 8 grams were placed in a ball mill and processed for 2 hours.
- particulates 8 grams were embedded in exfoliated graphite worm matrix and the resulting particulates were found to be typically ellipsoidal or potato-like shape.
- Cyanoethyl poly(vinyl alcohol) was prepared by gelation of a precursor solution, along with Si particles and graphene sheets).
- the precursor solution was composed of 2 wt. % PVA-CN (Shin-Etsu Chemical) dissolved in a liquid electrolyte consisting of 0.2M LiPF 6 in a liquid mixture of ethylene carbonate (EC)/dimethyl 40 carbonate (DMC)/ethylmethyl carbonate (EMC) with a volume ratio of 1:1:1.
- EC ethylene carbonate
- DMC dimethyl 40 carbonate
- EMC ethylmethyl carbonate
- Si particles investigated include micron-scale Si particles (2-3 ⁇ m in diameter), sub-micron Si plates (approximately 220 nm in thickness), and Si nanowires supplied from Angstron Energy Co. (Dayton, Ohio).
- a typical anode composition includes 85 wt. % active material (e.g., graphene-encapsulated polymer foam-protected Si or Co 3 O 4 particles), 7 wt. % acetylene black (Super-P), and 8 wt. % polyvinylidene fluoride binder (PVDF, 5 wt. % solid content) dissolved in N-methyl-2-pyrrolidinoe (NMP). After coating the slurries on Cu foil, the electrodes were dried at 120° C. in vacuum for 2 h to remove the solvent.
- active material e.g., graphene-encapsulated polymer foam-protected Si or Co 3 O 4 particles
- Super-P acetylene black
- PVDF polyvinylidene fluoride binder
- NMP N-methyl-2-pyrrolidinoe
- Cathode layers are made in a similar manner (using Al foil as the cathode current collector) using the conventional slurry coating and drying procedures.
- An anode layer, separator layer (e.g. Celgard 2400 membrane), and a cathode layer are then laminated together and housed in a plastic-Al envelop.
- the cell is then injected with 1 M LiPF 6 electrolyte solution dissolved in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) (EC-DEC, 1:1 v/v).
- EC-DEC ethylene carbonate
- EC-DEC diethyl carbonate
- ionic liquids were used as the liquid electrolyte.
- the cell assemblies were made in an argon-filled glove-box.
- the cyclic voltammetry (CV) measurements were carried out using an Arbin electrochemical workstation at a typical scanning rate of 1 mV/s.
- the electrochemical performances of various cells were also evaluated by galvanostatic charge/discharge cycling at a current density of from 50 mA/g to 10 A/g.
- galvanostatic charge/discharge cycling at a current density of from 50 mA/g to 10 A/g.
- multi-channel battery testers manufactured by LAND were used for long-term cycling tests.
- cycle life of a battery In lithium-ion battery industry, it is a common practice to define the cycle life of a battery as the number of charge-discharge cycles that the battery suffers 20% decay in capacity based on the initial capacity measured after the required electrochemical formation.
- FIG. 4 shows the charge-discharge cycling behaviors of 2 lithium cells featuring Co 3 O 4 particle-based anodes: one cell containing expanded graphite-embraced solid polymer-Co 3 O 4 particles (substantially no pores) and the other cell containing expanded graphite-encapsulated, polymer foam-protected Co 3 O 4 particles produced by the instant method (having a pore/anode particle volume ratio of 1.2/1.0). It is clear that the presently invented graphite-encapsulated, polymer foam-protected Co 3 O 4 particles exhibit significantly more stable battery cycle behavior.
- the cell containing graphite-encapsulated Co 3 O 4 particles (no polymer foam) has a cycle life of approximately 260 cycles, at which the capacity suffers a 20% decay.
- the cell featuring the EP-encapsulated, polymer foam-protected Co 3 O 4 particles prepared according to the instant disclosure experiences only a 10.44% reduction in capacity after 720 cycles.
- the cycle life is expected to exceed 1,400 cycles.
- a higher pore-to-anode active material ratio leads to a longer cycle life until when the ratio reaches approximately 1.9/1.0 for the Co 3 O 4 particle-based electrode.
- Shown in FIG. 5 are the charge-discharge cycling behaviors (specific capacity) of 3 lithium-ion cells each having SnO 2 particles as the an anode active material and CNTs (5% by weight) as a conductive reinforcement: one cell featuring exfoliated graphite worm-encapsulated SnO 2 particles having no pores between encapsulating graphite worm layer and SnO 2 particles; second cell having a polymer foam between the encapsulating exfoliated graphite worms and SnO 2 particles with a pore-to-SnO 2 volume ratio of 0.45/1.0; third cell having a polymer foam between the encapsulating exfoliated graphite worms and SnO 2 particles with a pore-to-SnO 2 volume ratio of 1.25/1.0.
- FIG. 7 shows the cycle life of a lithium-ion cell containing expanded graphite flake-encapsulated, CNT-reinforced polymer foam-assisted porous Si particles, plotted as a function of the total pore-to-solid ratio in the particulate.
Abstract
Description
- (1) reducing the size of the active material particle, presumably for the purpose of reducing the total strain energy that can be stored in a particle, which is a driving force for crack formation in the particle. However, a reduced particle size implies a higher surface area available for potentially reacting with the liquid electrolyte to form a higher amount of SEI. Such a reaction is undesirable since it is a source of irreversible capacity loss.
- (2) depositing the electrode active material in a thin film form directly onto a current collector, such as a copper foil. However, such a thin film structure with an extremely small thickness-direction dimension (typically much smaller than 500 nm, often necessarily thinner than 100 nm) implies that only a small amount of active material can be incorporated in an electrode (given the same electrode or current collector surface area), providing a low total lithium storage capacity and low lithium storage capacity per unit electrode surface area (even though the capacity per unit mass can be large). Such a thin film must have a thickness less than 100 nm to be more resistant to cycling-induced cracking, further diminishing the total lithium storage capacity and the lithium storage capacity per unit electrode surface area. Such a thin-film battery has very limited scope of application. A desirable and typical electrode thickness is from 100 μm to 200 μm. These thin-film electrodes (with a thickness of <500 nm or even <100 nm) fall short of the required thickness by three (3) orders of magnitude, not just by a factor of 3.
- (3) using a composite composed of small electrode active particles protected by (dispersed in or encapsulated by) a less active or non-active matrix, e.g., carbon-coated Si particles, sol gel graphite-protected Si, metal oxide-coated Si or Sn, and monomer-coated Sn nano particles. Presumably, the protective matrix provides a cushioning effect for particle expansion or shrinkage, and prevents the electrolyte from contacting and reacting with the electrode active material. Examples of high-capacity anode active particles are Si, Sn, and SnO2. Unfortunately, when an active material particle, such as Si particle, expands (e.g. up to a volume expansion of 380%) during the battery charge step, the protective coating is easily broken due to the mechanical weakness and/o brittleness of the protective coating materials. There has been no high-strength and high-toughness material available that is itself also lithium ion conductive.
-
- 1) As schematically illustrated in
FIG. 2(A) , in an anode composed of these high-capacity materials, severe pulverization (fragmentation of the alloy particles) occurs during the charge and discharge cycles due to severe expansion and contraction of the anode active material particles induced by the insertion and extraction of the lithium ions in and out of these particles. The expansion and contraction, and the resulting pulverization, of active material particles, lead to loss of contacts between active material particles and conductive additives and loss of contacts between the anode active material and its current collector. These adverse effects result in a significantly shortened charge-discharge cycle life. - 2) The approach of using a composite composed of small electrode active particles protected by (dispersed in or encapsulated by) a less active or non-active matrix, e.g., carbon-coated Si particles, sol gel graphite-protected Si, metal oxide-coated Si or Sn, and monomer-coated Sn nano particles, has failed to overcome the capacity decay problem. Presumably, the protective matrix provides a cushioning effect for particle expansion or shrinkage, and prevents the electrolyte from contacting and reacting with the electrode active material. Unfortunately, when an active material particle, such as Si particle, expands (e.g. up to a volume expansion of 380%) during the battery charge step, the protective coating is easily broken due to the mechanical weakness and/or brittleness of the protective coating materials. There has been no high-strength and high-toughness material available that is itself also lithium ion conductive.
- 3) The approach of using a core-shell structure (e.g. Si nano particle encapsulated in a carbon or SiO2 shell) also has not solved the capacity decay issue. As illustrated in upper portion of
FIG. 2(B) , a non-lithiated Si particle can be encapsulated by a carbon shell to form a core-shell structure (Si core and carbon or SiO2 shell in this example). As the lithium-ion battery is charged, the anode active material (carbon- or SiO2-encapsulated Si particle) is intercalated with lithium ions and, hence, the Si particle expands. Due to the brittleness of the encapsulating shell (carbon), the shell is broken into segments, exposing the underlying Si to electrolyte and subjecting the Si to undesirable reactions with electrolyte during repeated charges/discharges of the battery. These reactions continue to consume the electrolyte and reduce the cell's ability to store lithium ions. - 4) Referring to the lower portion of
FIG. 2(B) , wherein the Si particle has been pre-lithiated with lithium ions; i.e. has been pre-expanded in volume. When a layer of carbon (as an example of a protective material) is encapsulated around the pre-lithiated Si particle, another core-shell structure is formed. However, when the battery is discharged and lithium ions are released (de-intercalated) from the Si particle, the Si particle contracts, leaving behind a large gap between the protective shell and the Si particle. Such a configuration is not conducive to lithium intercalation of the Si particle during the subsequent battery charge cycle due to the gap and the poor contact of Si particle with the protective shell (through which lithium ions can diffuse). This would significantly curtail the lithium storage capacity of the Si particle particularly under high charge rate conditions.
- 1) As schematically illustrated in
-
- (a) Physical blowing agents: e.g. hydrocarbons (e.g. pentane, isopentane, cyclopentane), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and liquid CO2. The bubble/foam-producing process is endothermic, i.e. it needs heat (e.g. from a melt process or the chemical exotherm due to cross-linking), to volatize a liquid blowing agent.
- (b) Chemical blowing agents: e.g. isocyanate, azo-, hydrazine and other nitrogen-based materials (for thermoplastic and elastomeric foams), sodium bicarbonate (e.g. baking soda, used in thermoplastic foams). Here gaseous products and other by-products are formed by a chemical reaction, promoted by process or a reacting polymer's exothermic heat. Since the blowing reaction involves forming low molecular weight compounds that act as the blowing gas, additional exothermic heat is also released. Powdered titanium hydride is used as a foaming agent in the production of metal foams, as it decomposes to form titanium and hydrogen gas at elevated temperatures. Zirconium (II) hydride is used for the same purpose. Once formed the low molecular weight compounds will never revert to the original blowing agent(s), i.e. the reaction is irreversible.
- (c) Mixed physical/chemical blowing agents: e.g. used to produce flexible polyurethane (PU) foams with very low densities. Both the chemical and physical blowing can be used in tandem to balance each other out with respect to thermal energy released/absorbed; hence, minimizing temperature rise. For instance, isocyanate and water (which react to form CO2) are used in combination with liquid CO2 (which boils to give gaseous form) in the production of very low density flexible PU foams for mattresses.
- (d) Mechanically injected agents: Mechanically made foams involve methods of introducing bubbles into liquid polymerizable matrices (e.g. an unvulcanized elastomer in the form of a liquid latex). Methods include whisking-in air or other gases or low boiling volatile liquids in low viscosity lattices.
We have found that the above four mechanisms can all be used to create pores in the protecting polymer.
- (a) Formation of three immiscible chemical phases: liquid manufacturing vehicle phase, core material phase and encapsulation material phase. The core materials are dispersed in a solution of the encapsulating polymer (elastomer or its monomer or oligomer). The encapsulating material phase, which is an immiscible polymer in liquid state, is formed by (i) changing temperature in polymer solution, (ii) addition of salt, (iii) addition of non-solvent, or (iv) addition of an incompatible polymer in the polymer solution.
- (b) Deposition of encapsulation shell material: core material being dispersed in the encapsulating polymer solution, encapsulating polymer material coated around core particles, and deposition of liquid polymer embracing around core particles by polymer adsorbed at the interface formed between core material and vehicle phase; and
- (c) Hardening of encapsulating shell material: shell material being immiscible in vehicle phase and made rigid via thermal, cross-linking, or dissolution techniques.
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